KR20110057500A - Multi-layer biodegradable polyester film - Google Patents

Multi-layer biodegradable polyester film Download PDF

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KR20110057500A
KR20110057500A KR1020090113933A KR20090113933A KR20110057500A KR 20110057500 A KR20110057500 A KR 20110057500A KR 1020090113933 A KR1020090113933 A KR 1020090113933A KR 20090113933 A KR20090113933 A KR 20090113933A KR 20110057500 A KR20110057500 A KR 20110057500A
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resin layer
film
polyester film
biodegradable polyester
layer
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KR1020090113933A
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KR101045869B1 (en
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김경연
김상일
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에스케이씨 주식회사
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B11/00—Wrapping, e.g. partially or wholly enclosing, articles or quantities of material, in strips, sheets or blanks, of flexible material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

PURPOSE: A multi-layered biodegradable polyester film is provided to enable use for a general packing material, food packaging material, medicine packaging material due to excellent thermal adhesiveness as well as excellent moisture barrier property, mechanical property, and dimensional stability. CONSTITUTION: A multi-layered biodegradable polyester film includes: a base layer containing a crystalline polylactic acid-based polymer; a first resin layer which is formed at one side of the base layer and includes a polylactic acid-based polymer in which the content of D-lactic acid is 4 weight% or greater; and a second resin layer which is formed at the other side of the base layer and includes a homopolymer or copolymer of aliphatic or aromatic polyester.

Description

다층 생분해성 폴리에스터 필름{MULTI-LAYER BIODEGRADABLE POLYESTER FILM}Multilayer Biodegradable Polyester Film {MULTI-LAYER BIODEGRADABLE POLYESTER FILM}

본 발명은 일반포장재, 식품포장재, 약제포장재 등으로 사용될 수 있는 다층 생분해성 폴리에스터 필름에 관한 것이다.The present invention relates to a multilayer biodegradable polyester film that can be used as general packaging, food packaging, pharmaceutical packaging and the like.

열접착이 가능하고 수분 투과도가 낮은 범용 플라스틱 필름으로는, 석유계로부터 유래된 폴리비닐클로라이드(PVC), 폴리에틸렌(PE), 폴리프로필렌(PP)을 들 수 있다. 그러나, 폴리비닐클로라이드 필름은 소각시 다이옥신 등과 같은 유해물질이 발생하여 사용이 규제되고 있고, 폴리에틸렌 필름은 치수안정성이 불량하고 기계적 특성이 너무 낮아 저급 포장 봉지 이외에는 사용이 제한된다. 폴리프로필렌 필름은 비교적 안정한 분자 구조로 양호한 기계적 특성을 지녔으나, 포장 용도로 사용된 후 대부분 매립 처리되며, 이 경우 화학적, 생물적 안정성 때문에 거의 분해되지 않고 축적되어 매립지의 수명을 짧게하고 토양 오염 문제를 야기하게 된다. Examples of general-purpose plastic films capable of thermal bonding and low water permeability include polyvinyl chloride (PVC), polyethylene (PE) and polypropylene (PP) derived from petroleum. However, the use of polyvinyl chloride film is regulated by the generation of harmful substances such as dioxins during incineration, and polyethylene film is limited in use except low-grade packaging bags because of poor dimensional stability and too low mechanical properties. Polypropylene film has good mechanical properties due to its relatively stable molecular structure, but it is mostly landfilled after being used for packaging purposes, in which case it accumulates almost without decomposition due to chemical and biological stability, which shortens the landfill's lifespan and causes soil contamination. Will cause.

이와 같이 분해가 되지 않는 플라스틱의 단점을 보완하기 위해, 난분해성 플라스틱에 전분 등과 같은 분해성 수지를 20 내지 40 ％ 혼합하여 일정 기간이 경과 하면 분해가 되도록 만든 필름이 생산되고 있으나, 이러한 필름은 혼합된 분해성 수지의 영향으로 기계적 특성과 배리어(barrier) 특성이 저하되고, 열접착성이 약하다는 단점이 있다. In order to compensate for the disadvantages of plastics that cannot be decomposed as described above, a film made of 20 to 40% of a decomposable resin such as starch and the like is decomposed after a predetermined period of time has been produced. Under the influence of the decomposable resin, mechanical and barrier properties are lowered, and heat adhesiveness is weak.

따라서, 최근에는 생분해성이 있는 지방족 폴리에스터인 폴리락트산에 관한 연구가 많이 진행되고 있다. 그러나, 폴리락트산 고유의 결정구조로 인하여, 저온 열접착성과 수분 배리어성이 불량하여 포장용으로 그 용도가 제한적이며, 열접착성을 주기 위해 폴리에틸렌이나 폴리프로필렌으로 라미네이팅하여 실링성을 부여할 수 있으나, 친환경 차원에서 완전하게 생분해가 불가능하다는 문제점이 있고, 수분 배리어성을 주기 위해 알루미늄 호일을 합지하더라도 최종적으로는 생분해가 불가능하다는 문제점이 있다.Therefore, in recent years, much research is being conducted on polylactic acid, which is a biodegradable aliphatic polyester. However, due to the inherent crystal structure of polylactic acid, its low temperature thermal adhesiveness and moisture barrier property are poor, so its use is limited for packaging, and in order to give thermal adhesiveness, it may be laminated with polyethylene or polypropylene to impart sealing property. There is a problem that completely biodegradation is impossible in terms of eco-friendliness, and even if the aluminum foil is laminated in order to give a moisture barrier property, there is a problem in that biodegradation is impossible.

일본 특허공개 평10-24518호 및 평10-138433호는 폴리락트산계 중합체를 주성분으로 하고 일면에 규소 산화물로 투명 증착하여 가스 배리어성이 우수한 연신 필름을 제공하고 있다. 그러나, 이는 투명성은 유지할 수 있어도 약간의 구김이나 충격에도 박막층이 쉽게 깨져 충분한 수분 및 가스 배리어성을 제공할 수 없다는 단점이 있다.Japanese Patent Application Laid-Open Nos. 10-24518 and 10-138433 provide stretched films having excellent gas barrier properties by transparent vapor deposition of silicon oxide on one surface of a polylactic acid polymer. However, this has the disadvantage that the thin film layer is easily broken even with slight wrinkles or impacts, even though transparency can be maintained, and thus cannot provide sufficient moisture and gas barrier properties.

일본 특허공개 제2005-2224호는, 디올체를 포함하는 방향족 폴리에스터 공중합체에 팽창성 층상규산염을 분산시켜 가스 배리어성을 향상시킨 생분해성 필름을 제공하고 있다. 그러나, 층상규산염은 판상형태의 무기광물로서 필름에 균일하게 분산되기 어렵고, 가스 배리어성에 효과가 있을 수 있으나 수분 배리어성에는 효과가 좋지 않으며, 쉽게 응집하여 표면으로 돌출됨에 따라 알루미늄 증착시 균일하게 증착되지 않고, 표면의 요철로 인해 열접착성이 현저히 떨어지는 단점이 있다.Japanese Patent Laid-Open No. 2005-2224 provides a biodegradable film in which an expandable layered silicate is dispersed in an aromatic polyester copolymer containing a diol body to improve gas barrier properties. However, the layered silicate is a plate-shaped inorganic mineral that is difficult to be uniformly dispersed in the film, and may have an effect on the gas barrier property, but is not effective on the moisture barrier property, and is uniformly deposited during aluminum deposition as it easily protrudes to the surface. Rather, there is a disadvantage that the heat adhesion is significantly lowered due to the irregularities of the surface.

일본 특허공개 제2008-62586호는, 스테레오컴플렉스 폴리락트계 중합체를 주성분으로 하고 일면에 폴리비닐알콜을 코팅한 가스 배리어성의 필름을 제공하고 있다. 그러나, 고융점과 고결정성인 스테레오컴플렉스 폴리락트산만으로는 실제적으로 가스 배리어성이 향상되기 어렵고, 폴리비닐알콜은 산소투과도에 유리할 수 있으나 강한 극성기를 가지고 있어 수분에 노출됐을 때 수분투과도와 가스투과도가 급격히 불량해지는 단점이 있으며, 열접착성이 떨어진다.Japanese Patent Laid-Open No. 2008-62586 provides a gas barrier film in which a polyvinyl alcohol is coated on one surface with a stereocomplex polylactic polymer as a main component. However, the high melting point and high crystalline stereocomplex polylactic acid alone is not practical to improve the gas barrier property, and polyvinyl alcohol may be advantageous to oxygen permeability, but has a strong polarity, so that water permeability and gas permeability are rapidly increased when exposed to moisture. There is a disadvantage in that it is poor, and heat adhesiveness is poor.

따라서, 본 발명의 목적은, 열접착성이 우수하면서 수분 배리어성, 기계적 특성, 치수안정성 등이 우수한 다층 생분해성 폴리에스터 필름 및 이를 포함하는 포장재를 제공하는 것이다.Accordingly, it is an object of the present invention to provide a multilayer biodegradable polyester film having excellent thermal adhesiveness and excellent moisture barrier properties, mechanical properties, dimensional stability, and the like and a packaging material including the same.

상기 목적에 따라 본 발명은, 결정성 폴리락트산계 중합체를 함유하는 기재층, 상기 기재층의 일면에 형성되고 D-락트산 함량이 4중량% 이상인 폴리락트산계 중합체를 함유하는 제1수지층, 및 상기 기재층의 다른 일면에 형성되고 지방족 또는 방향족 폴리에스터의 단독중합체 또는 공중합체를 함유하는 제2수지층을 포함하는 구성을 가지며, 전체 필름에 대한 폴리락트산계 중합체의 함량이 50 내지 99 중량%이고, 상기 제1수지층 및 제2수지층 중 적어도 한 층의 열접착강도가 500gf/inch 이상인, 다층 생분해성 폴리에스터 필름을 제공한다.According to the above object, the present invention provides a substrate layer containing a crystalline polylactic acid polymer, a first resin layer formed on one surface of the substrate layer and containing a polylactic acid polymer having a D-lactic acid content of 4% by weight or more, and It is formed on the other side of the base layer and has a configuration comprising a second resin layer containing a homopolymer or copolymer of aliphatic or aromatic polyester, the content of the polylactic acid polymer to the total film is 50 to 99% by weight The thermal adhesive strength of at least one of the first resin layer and the second resin layer is 500gf / inch or more, to provide a multi-layer biodegradable polyester film.

또한, 본 발명은 상기 다층 생분해성 폴리에스터 필름을 포함하는 포장재를 제공한다.The present invention also provides a packaging material comprising the multilayer biodegradable polyester film.

본 발명에 따르는 필름은 열접착성, 증착 후의 수분배리어성, 기계적 특성, 치수안정성 등의 목적하는 제반 물성이 우수하므로, 일반포장재, 식품포장재, 약제포장재 용도에 폭 넓게 사용될 수 있다.Since the film according to the present invention has excellent desired physical properties such as thermal adhesiveness, moisture barrier property after deposition, mechanical properties, dimensional stability, and the like, it can be widely used for general packaging materials, food packaging materials, and pharmaceutical packaging materials.

이하, 본 발명에 대해 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명에 따르는 다층 생분해성 폴리에스터 필름은, 결정성 폴리락트산계 중합체를 함유하는 기재층, 상기 기재층의 일면에 형성되고 D-락트산 함량이 4중량% 이상인 폴리락트산계 중합체를 함유하는 제1수지층, 및 상기 기재층의 다른 일면에 형성되고 지방족 또는 방향족 폴리에스터의 단독중합체 또는 공중합체를 함유하는 제2수지층을 포함한다.A multilayer biodegradable polyester film according to the present invention is a substrate layer containing a crystalline polylactic acid polymer, a first formed on one side of the substrate layer and containing a polylactic acid polymer having a D-lactic acid content of 4% by weight or more. And a second resin layer formed on the other side of the base layer and containing a homopolymer or copolymer of aliphatic or aromatic polyester.

본 발명에 있어서, 적층필름 전체 중 폴리락트산계 중합체가 50 내지 99 중량%으로 포함될 필요가 있다. 상기 범위 내에서 본 발명이 목적하는 제반 물성을 달성할 수 있는데, 특히 폴리락트산계 중합체가 50중량% 미만이면 필름가공시, 기재층과 제1 및 제2수지층과의 연신응력이 발생하여 층간의 박리가 일어나 가공성이 떨어지고 일반 포장재로서 사용할 수 없다. 더욱 바람직하게는, 폴리락트산계 중합체가 70 내지 90 중량%로 포함되는 것이 좋다.In the present invention, it is necessary to include 50 to 99% by weight of the polylactic acid polymer in the whole laminated film. Within the above range, the desired physical properties of the present invention can be achieved. Particularly, when the polylactic acid polymer is less than 50% by weight, the stretching stress between the base layer and the first and second resin layers is generated during film processing. Peeling occurs, resulting in poor workability and cannot be used as a general packaging material. More preferably, the polylactic acid-based polymer is included in 70 to 90% by weight.

또한, 필름의 제1수지층 및 제2수지층 중 적어도 한 층의 열접착 강도가 500gf/inch 이상일 필요가 있다. 열접착 강도가 500gf/inch 미만이면 열접착성이 불량하여 접착층 사이에 밀착성이 떨어져 박리현상에 일어날 수 있어 포장용도로 사용시 접착층 사이에 벌어진 틈으로 내용물이 새거나 실링부위에서 파단이 생길 수 있다. 열접착강도가 500gf/inch 이상이면, 열 접착 필름 용도로 가능하며, 가공상 문제가 없다. 더욱 바람직하게는 제1수지층 및 제2수지층 중 적어도 한 층의 열접착 강도가 800 내지 1200 gf/inch 인 것이 좋다.In addition, the thermal adhesive strength of at least one of the first resin layer and the second resin layer of the film needs to be 500 gf / inch or more. If the thermal adhesive strength is less than 500gf / inch, poor thermal adhesiveness may result in poor adhesion between the adhesive layers, which may result in peeling, and when used for packaging, the contents may leak or break in the sealing part due to gaps between the adhesive layers. If the thermal adhesive strength is 500gf / inch or more, it is possible to use the thermal adhesive film, there is no problem in processing. More preferably, the heat adhesive strength of at least one of the first resin layer and the second resin layer is 800 to 1200 gf / inch.

본 발명의 필름의 제1수지층에 함유되는 폴리락트산계 중합체는, 중합체 중량을 기준으로 할 때 D-락트산 함량이 4중량% 이상인 것이 바람직하다. D-락트산 함량이 4중량% 미만일 경우, 폴리락트산의 결정성이 너무 높아져 저온 열접착성을 구현하기 어려울 수 있고, 열접착을 하기 위해 고온에서 실링할 경우 가공시 원단에 변형이 일어날 수 있다. 더욱 바람직하게는 9 내지 12 중량% 인 것이 좋다.The polylactic acid polymer contained in the first resin layer of the film of the present invention preferably has a D-lactic acid content of 4% by weight or more based on the polymer weight. If the D-lactic acid content is less than 4% by weight, the crystallinity of the polylactic acid may be too high to realize low temperature heat adhesiveness, and deformation may occur in the fabric during processing when sealing at high temperature for heat bonding. More preferably 9 to 12% by weight.

또한, 본 발명의 필름의 기재층에 포함되는 결정성 폴리락트산계 중합체는 D-락트산 함량이 1.0 내지 10.0 중량%이고, 용융온도가 140 내지 230 ℃인 것이 바람직하나, 이에 한정되는 것은 아니다.In addition, the crystalline polylactic acid polymer included in the base layer of the film of the present invention preferably has a D-lactic acid content of 1.0 to 10.0 wt%, and a melting temperature of 140 to 230 ° C, but is not limited thereto.

본 발명의 적층필름은, 제1수지층 및 제2수지층 중 적어도 한 층에, 바람직하게는 제2수지층에, 알루미늄 산화물, 규소 산화물, 알루미나 산화물 등이 증착된 형태로 가공되는 것이 가능하다.The laminated film of the present invention can be processed into a form in which aluminum oxide, silicon oxide, alumina oxide, or the like is deposited on at least one of the first resin layer and the second resin layer, preferably on the second resin layer. .

본 발명의 적층필름은, 제1수지층 및 제2수지층 중 적어도 한 층에 알루미늄을 증착시켰을 경우의 알루미늄과 필름과의 증착강도가 200gf/inch 이상인 것이 바람직하다. 200gf/inch 미만이면 알루미늄 증착강도가 너무 약해서 증착 박막이 쉽게 벗겨지므로, 수분 배리어성이 나빠질 수 있다. 더욱 바람직하게는 600 내지 800 gf/inch 인 것이 좋다.In the laminated film of the present invention, when the aluminum is deposited on at least one of the first resin layer and the second resin layer, the deposition strength of aluminum and the film is preferably 200 gf / inch or more. If the thickness is less than 200 gf / inch, the aluminum deposition strength is so weak that the deposited thin film is easily peeled off, and thus the moisture barrier property may be deteriorated. More preferably, it is 600 to 800 gf / inch.

또한, 제1수지층 및 제2수지층 중 적어도 한 층에 알루미늄을 증착했을 경우의 수분투과도가 38℃, 상대습도 90% 조건에서 20g/㎡·day·atm 이하인 것이 바람직하다. 수분투과도가 20g/㎡·day·atm 초과이면, 하절기와 같은 습한 환경에서 내용물이 수분에 의해 눅눅해지거나 쉽게 상할 수 있어서 유통기간이 긴 일반식품 이나 약제의 포장재로 사용하기가 곤란할 수 있다 더욱 바람직하게는 0.1 내지 10 g/㎡·day·atm 인 것이 좋다.Moreover, it is preferable that the water transmittance at the time of depositing aluminum to at least one of the 1st resin layer and the 2nd resin layer is 20 g / m <2> * day * atm or less on 38 degreeC and 90% of a relative humidity. If the moisture permeability is greater than 20 g / m 2 · day · atm, the contents may be damp or easily damaged by moisture in a humid environment such as summer, which may make it difficult to use as a packaging material for general foods or pharmaceuticals with a long shelf life. Preferably it is 0.1-10 g / m <2> * day * atm.

또한, 100℃, 5분 열풍조건에서 종방향과 횡방향의 열수축률이 모두 20% 이하인 것이 바람직하다. 20% 초과일 경우, 인쇄나 라미네이트시에 열풍에 의한 폭방향, 길이방향 수축이 심하여 인쇄상 문제가 발생하고 인쇄 후 컬 발생이 심하여 말리는 현상이 있을 수 있다. 더욱 바람직하게는 0 내지 20 %인 것이 좋다Moreover, it is preferable that the thermal contraction rate of a longitudinal direction and a lateral direction is 20% or less in 100 degreeC and 5-minute hot wind conditions. If it exceeds 20%, there may be a printing problem due to severe shrinkage in the width direction and the lengthwise direction due to hot air during printing or lamination, and curling may occur after printing. More preferably 0 to 20% is good.

또한, 제2수지층에 포함되는 지방족 폴리에스터로서는, 하기 화학식 1 내지 3 중 하나 이상의 반복단위를 포함하는 단독중합체 또는 랜덤블록 공중합체인 것을 사용할 수 있다. In addition, as the aliphatic polyester included in the second resin layer, a homopolymer or a random block copolymer containing one or more repeating units of the following Chemical Formulas 1 to 3 may be used.

Figure 112009072163170-PAT00001
Figure 112009072163170-PAT00001

Figure 112009072163170-PAT00002
Figure 112009072163170-PAT00002

Figure 112009072163170-PAT00003
Figure 112009072163170-PAT00003

상기 화학식 1 및 2에서, R1은 C1-3알킬이고, R2는 C1-7알킬이며, 바람직하게는, R1은 메틸 또는 에틸이고, R2는 에틸, 프로필, 펜틸 또는 헵틸이다.In Formulas 1 and 2, R 1 is C 1-3 alkyl, R 2 is C 1-7 alkyl, preferably, R 1 is methyl or ethyl, and R 2 is ethyl, propyl, pentyl or heptyl .

상기 화학식 1 및 2 중 하나 이상의 반복단위를 포함하는 단독중합체 또는 공중합체로서는, 폴리하이드록시알카노에이트(PHAs)를 들 수 있으며, 알킬기(R1 및 R2)에 따라 다양한 중합체를 구성할 수 있는데, 예를 들어, 폴리하이드록시부티레이트(polyhydroxybutyrate, PHB), 폴리-3-하이드록시발러레이트(poly-3-hydroxyvalerate, PBV), 폴리하이드록시부티레이트 발러레이트(polyhydroxybutyrate valerate, PHBV), 폴리-3-하이드록시부티레이트-코-3-하이드록시발러레이트(poly-(3-hydroxybutyrate-co-3-hydroxyvalerate), P(3HB-co-3HV)), 폴리-3-하이드록시부티레이트-코-3-하이드록시헥사노에이트(poly-(3-hydroxybutyrate-co-3-hydroxyhexanoate), P(3HB-co-3HH)) 등의 단독중합체 또는 공중합체 형태로 존재할 수 있으며, 이들 중 1종 이상이 사용될 수 있다. Examples of the homopolymer or copolymer including one or more repeating units of Formulas 1 and 2 include polyhydroxyalkanoate (PHAs), and various polymers may be formed according to alkyl groups (R 1 and R 2 ). For example, polyhydroxybutyrate (PHB), poly-3-hydroxyvalerate (PBV), polyhydroxybutyrate valerate (PHBV), poly-3 -Hydroxybutyrate-co-3-hydroxyvalerate (poly- (3-hydroxybutyrate-co-3-hydroxyvalerate), P (3HB-co-3HV)), poly-3-hydroxybutyrate-co-3- May be present in the form of homopolymers or copolymers such as hydroxyhexanoate (poly- (3-hydroxybutyrate-co-3-hydroxyhexanoate), P (3HB-co-3HH)), and one or more of these may be used. have.

상기 화학식 3의 반복단위를 포함하는 중합체로서는, 선형 지방족 폴리에스터인 글리콜라이드(glycolide)가 축중합된 폴리글리콜산(PGA)을 단독으로 사용할 수 있다. As the polymer including the repeating unit of Formula 3, polyglycolic acid (PGA) polycondensed with glycolide, which is a linear aliphatic polyester, may be used alone.

또한, 제2수지층에 포함되는 방향족 폴리에스터계 수지로서는, 방향족 디카복실산을 주성분으로 하는 산 성분과 C1-10알킬렌글리콜을 주성분으로 하는 글리콜 성분이 중축합된 수지를 사용할 수 있다. 상기 방향족 디카복실산의 구체적인 예 로는 테레프탈산, 디메틸테레프탈레이트, 이소프탈산, 디메틸이소프탈레이트, 나프탈렌디카복실산, 나프탈렌디카복실레이트 등을 들 수 있으며, 다른 방향족 디카복실산 성분과 공중합하여 사용할 수도 있다. 상기 알킬렌글리콜의 구체적인 예로서는 에틸렌글리콜, 1,3-프로판디올, 테트라메틸렌글리콜, 1,4-시클로헥산디메탄올, 네오펜틸글리콜, 2-메틸-1,3-프로판디올, 디에틸렌글리콜 등을 들 수 있으며, 다른 글리콜 성분을 포함하여 이들을 서로 공중합하여 사용할 수도 있다. As the aromatic polyester resin contained in the second resin layer, a resin obtained by polycondensation of an acid component containing aromatic dicarboxylic acid as a main component and a glycol component containing C 1-10 alkylene glycol as a main component can be used. Specific examples of the aromatic dicarboxylic acid include terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, naphthalenedicarboxylic acid, naphthalenedicarboxylate, and the like, and may be used by copolymerizing with other aromatic dicarboxylic acid components. Specific examples of the alkylene glycol include ethylene glycol, 1,3-propanediol, tetramethylene glycol, 1,4-cyclohexanedimethanol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol, and the like. And other glycol components, and these may be copolymerized with each other.

본 발명의 폴리에스터계 수지의 제조시 공지의 첨가제, 예를 들면 중축합촉매, 분산제, 정전인가제, 대전방지제, 자외선 차단제, 블로킹방지제 및 기타 무기활제를 본 발명의 효과를 손상시키지 않는 범위 내에서 첨가하여도 무방하다. 예를 들어, 슬립성을 위하여 이산화규소의 미세분말을 혼합첨가하여 제조할 수 있다.Known additives, such as polycondensation catalysts, dispersants, antistatic agents, antistatic agents, sunscreens, antiblocking agents and other inorganic lubricants, in the preparation of the polyester resins of the present invention do not impair the effects of the present invention. It may be added from. For example, the fine powder of silicon dioxide may be mixed and added for slipping.

본 발명의 다층 생분해성 폴리에스터 필름은, 총 두께가 10 내지 200 ㎛인 것이 바람직하며, 각층별 두께로는 제1수지층(A)이 1 내지 30 ㎛이고 기재층(B)이 8 내지 140 ㎛이며 제2수지층(C)이 1 내지 30 ㎛인 것이 바람직하나, 이에 한정되지는 않는다.It is preferable that the multilayer biodegradable polyester film of this invention is 10-200 micrometers in total thickness, As each layer thickness, the 1st resin layer (A) is 1-30 micrometers, and the base material layer (B) is 8-140 Preferably, the second resin layer (C) is 1 to 30 µm, but is not limited thereto.

상기의 조성으로 적층 필름을 제조하는 방법에 있어서, 공압출 공정을 이용하는 것이 바람직하다. In the method of manufacturing a laminated | multilayer film by said composition, it is preferable to use a coextrusion process.

구체적으로, 먼저 제1수지층(A), 기재층(B), 및 제2수지층(C)의 수지를 각각 형성한 다음, 이들을 각각 융점 +30℃ 이상에서 용융시킨 후, 피드 블록을 사용하여 3층 (A/B/C)으로 적층하여 압출다이를 통해 토출해 낸다. 이어서 냉각드럼에서 제1수지층(A) 또는 제2수지층(C)을 드럼면으로 하여 정전 인가하면서 냉각시켜 미연신된 적층시트를 얻는다. Specifically, first, the resins of the first resin layer (A), the substrate layer (B), and the second resin layer (C) are respectively formed, and then they are respectively melted at a melting point of + 30 ° C. or higher, and then a feed block is used. 3 layers (A / B / C), and discharged through an extrusion die. Subsequently, in the cooling drum, the first resin layer (A) or the second resin layer (C) is cooled while electrostatically applying the drum surface to obtain an unstretched laminated sheet.

얻어진 미연신 적층시트를 용도에 따라 제품에 요구되는 연신비에 맞추어 통상 축차로 2축 연신 후 열고정 및 이완 공정을 거쳐 제조할 수 있다.The obtained non-stretched laminated sheet can be manufactured through a heat setting and a relaxation process after biaxial stretching in a sequential order according to the draw ratio required for the product according to the use.

이와 같은 본 발명에 따르는 필름은 열접착성, 증착 후의 수분배리어성, 기계적 특성, 치수안정성 등 본 발명이 목적으로 하는 제반 물성이 우수하므로, 일반포장재, 식품포장재, 약제포장재 용도에 폭 넓게 사용될 수 있다.Such a film according to the present invention has excellent physical properties such as heat adhesiveness, moisture barrier property after deposition, mechanical properties, dimensional stability, etc., and thus can be widely used for general packaging materials, food packaging materials, and pharmaceutical packaging materials. have.

이하, 실시예에 의하여 본 발명을 더욱 상세히 설명한다. 단, 하기의 실시예는 본 발명의 예시일 뿐 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only examples of the present invention and the present invention is not limited thereto.

실시예 1 Example 1

제1수지층(A)으로서 D-락트산 함량이 12중량%이고 용융온도가 존재하지 않는 비결정성 폴리락트산 수지를 사용하고, 기재층(B)으로서 용융온도가 165℃인 폴리락트산 수지에 평균입경 2㎛의 이산화규소를 혼합첨가시킨 마스터배치 수지를 최종필름의 0.07중량% 비율이 되도록 블렌딩한 수지를 사용하며, 제2수지층(C)으로서 폴리글리콜산(PGA, Kureha사)을 사용하였디. As the first resin layer (A), an amorphous polylactic acid resin having a D-lactic acid content of 12% by weight and no melting temperature is used, and an average particle diameter of the polylactic acid resin having a melting temperature of 165 ° C as the base layer (B). A resin blended with 2 μm of silicon dioxide mixed with a masterbatch resin in a ratio of 0.07% by weight of the final film was used, and polyglycolic acid (PGA, Kureha) was used as the second resin layer (C). .

상기 각각의 원료수지를 3개의 압출기를 통하여 기어 펌프량을 조절하여 A층, B층, 및 C층의 두께비가 3 : 5 : 2가 되도록 용융압출시킨 다음 피드 블록에서 3층으로 적층하였다.The raw material resin was melt-extruded to adjust the gear pump amount through three extruders so that the thickness ratio of A, B and C layers was 3: 5: 2, and then laminated in three layers in the feed block.

미연신 적층시트를 티다이 및 2축 연신 장치를 이용하여 종방향 연신비 3.0배로 75℃에서 연신하고, 횡방향 연신비 3.8배로 90℃에서 연신한 후, 149℃에서 열고정한 후 3% 이완을 주어, 20㎛의 두께를 가진 다층 폴리에스터 필름을 얻었다.The unstretched laminated sheet was stretched at 75 ° C. with a longitudinal stretching ratio of 3.0 times using a T-die and a biaxial stretching apparatus, stretched at 90 ° C. with a transverse stretching ratio of 3.8 times, then heat-set at 149 ° C., and then given 3% relaxation. A multilayer polyester film with a thickness of 20 μm was obtained.

실시예 2 Example 2

제1수지층(A)과 기재층(B)으로서 상기 실시예 1과 같은 수지를 사용하고, 제2수지층(C)으로서 사이클로헥산디메탄올(CHDM)이 60몰%으로 공중합된 글리콜계 변성 폴리에틸렌테레프탈레이트(PETG, SKC사)를 사용하여, 실시예 1과 같은 방식으로 3층 공압출하여 미연신 적층시트를 얻었다. Glycol-based modification in which the same resin as in Example 1 was used as the first resin layer (A) and the base material layer (B), and cyclohexanedimethanol (CHDM) was copolymerized at 60 mol% as the second resin layer (C). Using polyethylene terephthalate (PETG, SKC), three-layer co-extrusion in the same manner as in Example 1 to obtain an unoriented laminated sheet.

상기 미연신 적층시트를 종방향 연신비 3.0배로 60℃에서 연신하고, 횡방향 연신비 4.6배로 90℃에서 연신한 후, 130℃에서 열고정한 후 0.5%이완을 주어, 20㎛의 두께를 가진 다층 폴리에스터 필름을 얻었다.The unstretched laminated sheet was stretched at 60 ° C. with a longitudinal draw ratio of 3.0 times, at 90 ° C. with a lateral stretch ratio of 4.6, then heat-set at 130 ° C. and gave 0.5% relaxation to give a multilayer polyester having a thickness of 20 μm. A film was obtained.

실시예 3 Example 3

제1수지층(A)과 기재층(B)으로서 상기 실시예 1과 같은 수지를 사용하고, 제 2수지층(C)으로서 폴리하이드록시알카노에이트(PHAs, 알킬기: CH3 및 CH2CH2CH3, P(3HB-co-3HH)), Danimer scientific사)를 사용하여, 실시예 1과 같은 방식으로 3층 공압출하여 미연신 적층시트를 얻었다. As the first resin layer (A) and the base material layer (B), the same resin as in Example 1 was used, and as the second resin layer (C), polyhydroxyalkanoate (PHAs, alkyl groups: CH 3 and CH 2 CH) 2 CH 3 , P (3HB-co-3HH)) and Danimer Scientific Co.) were used to co-extrude three layers in the same manner as in Example 1 to obtain an unoriented laminate sheet.

상기 미연신 적층시트를 종방향 연신비 2.5배로 60℃에서 연신하고, 횡방향 연신비 4.6배로 70℃에서 연신한 후, 150℃에서 열고정한 후 3% 이완을 주어, 20㎛의 두께를 가진 다층 폴리에스터 필름을 얻었다.The unstretched laminated sheet was stretched at 60 ° C. at 2.5 times in the longitudinal drawing ratio, stretched at 70 ° C. at 4.6 times in the transverse direction, then heat-set at 150 ° C., and gave 3% relaxation to give a multilayer polyester having a thickness of 20 μm. A film was obtained.

비교예 1 Comparative Example 1

제1수지층(A)과 기재층(B)으로서 D-락트산 함량이 12중량%이고 용융온도가 존재하지 않는 비결정성의 폴리락트산 수지를 사용하고, 제2수지층(C)으로서 CHDM 60몰%으로 공중합한 글리콜계 변성 폴리에틸렌테레프탈레이트(PETG, SKC사)를 사용하여, 실시예 1과 같은 방식으로 3층 공압출하여 미연신 적층시트를 얻었다. As the first resin layer (A) and the base layer (B), an amorphous polylactic acid resin having a D-lactic acid content of 12% by weight and no melting temperature is used, and 60 mol of CHDM as the second resin layer (C). Using a glycol-based modified polyethylene terephthalate (PETG, SKC) copolymerized in%, three-layer co-extrusion in the same manner as in Example 1 to obtain an unoriented laminated sheet.

상기 미연신 적층시트를 종방향 연신비 2.5배로 50℃에서 연신하고, 횡방향 연신비 3.6배로 70℃에서 연신한 후, 90℃에서 열고정한 후 3% 이완을 주어, 20㎛의 두께를 가진 다층 폴리에스터 필름을 얻었다.The unstretched laminated sheet was stretched at 50 ° C. with 2.5 times the longitudinal draw ratio, stretched at 70 ° C. with 3.6 times the transverse draw ratio, and heat-set at 90 ° C. to give 3% relaxation, thereby giving a multilayer polyester having a thickness of 20 μm. A film was obtained.

비교예 2 Comparative Example 2

기재층(B) 및 제2수지층(C)으로서 상기 실시예 1과 같은 수지를 사용하고, 제1수지층(A)으로서 D-락트산 함량이 1.5%인 결정성 폴리락트산수지를 사용하여, 실시예 1과 같은 방식으로 3층 공압출하여 미연신 적층시트를 얻었다. Using the same resin as Example 1 as the base material layer (B) and the second resin layer (C), and using the crystalline polylactic acid resin having a D-lactic acid content of 1.5% as the first resin layer (A), Three-layer coextrusion was carried out in the same manner as in Example 1 to obtain an unstretched laminated sheet.

상기 미연신 적층시트를 종방향 연신비 3.0배로 85℃에서 연신하고, 횡방향 연신비 3.8배로 95℃에서 연신한 후, 160℃에서 열고정한 후 3% 이완을 주어, 20㎛의 두께를 가진 다층 폴리에스터 필름을 얻었다.The unstretched laminated sheet was stretched at 85 ° C. with a longitudinal stretch ratio of 3.0 times, at 95 ° C. with a lateral stretch ratio of 3.8 times, then heat-set at 160 ° C., and then gave 3% relaxation to give a multilayer polyester having a thickness of 20 μm. A film was obtained.

비교예 3 Comparative Example 3

기재층(B)으로서 상기 실시예 1과 같은 수지를 사용하고, 제1수지층(A) 및 제2수지층(C)으로서 1,3-프로판디올과 테레프탈레이트가 중합된 폴리트리메틸렌테레프탈레이트(PTT, Shell사)를 사용하여, 실시예 1과 같은 방식으로 3층 공압출하여 미연신 적층시트를 얻었다. Polytrimethylene terephthalate in which 1,3-propanediol and terephthalate were polymerized as the first resin layer (A) and the second resin layer (C), using the same resin as the base layer (B). (PTT, Shell, Inc.) was used to co-extrude three layers in the same manner as in Example 1 to obtain an unstretched laminated sheet.

상기 미연신 적층시트를 종방향 연신비 2.5배로 50℃에서 연신하고, 횡방향 연신비 3.6배로 70℃에서 연신한 후, 160℃에서 열고정한 후 3% 이완을 주어, 20㎛의 두께를 가진 다층 폴리에스터 필름을 얻었다.The unstretched laminated sheet was stretched at 50 ° C. with 2.5 times the longitudinal draw ratio, stretched at 70 ° C. with 3.6 times the lateral stretch ratio, and heat-set at 160 ° C. to give 3% relaxation, thereby giving a multilayer polyester having a thickness of 20 μm. A film was obtained.

비교예 4 Comparative Example 4

제1수지층(A) 및 기재층(B)으로서 상기 실시예 1과 같은 수지를 사용하고, 제2수지층(B)으로서 용융온도가 165℃인 폴리락트산 수지를 사용하여, 실시예 1과 같은 방식으로 3층 공압출하여 미연신 적층시트를 얻었다. As the first resin layer (A) and the base material layer (B), the same resin as in Example 1 was used, and as the second resin layer (B), a polylactic acid resin having a melting temperature of 165 ° C was used. Three-layer coextrusion was carried out in the same manner to obtain an unstretched laminated sheet.

상기 미연신 적층시트를 종방향 연신비 3.0배로 70℃에서 연신하고, 횡방향 연신비 3.8배로 85℃에서 연신한 후, 160℃에서 열고정한 후 3% 이완을 주어, 20㎛의 두께를 가진 다층 폴리에스터 필름을 얻었다.The unstretched laminated sheet was stretched at 70 ° C. with a longitudinal draw ratio of 3.0 times, stretched at 85 ° C. with a lateral stretch ratio of 3.8 times, and heat-set at 160 ° C. to give 3% relaxation, thereby giving a multilayer polyester having a thickness of 20 μm. A film was obtained.

시험예Test Example

상기 실시예 1 내지 3 및 비교예 1 내지 3에서 얻은 각각의 필름에 대해 다음과 같은 방법으로 특성을 측정하여 하기 표 1에 나타내었다.The properties of the films obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were measured in the following manners, and are shown in Table 1 below.

(1) D-락트산 함량(1) D-lactic acid content

자동 편광계(P-1020 Automatic Polarimeter, JASCO사)를 이용하여, 나트륨 램프 광원으로 589nm 파장에서 측정하여 소프트웨어로 계산하였다.Using an automatic polarimeter (P-1020 Automatic Polarimeter, JASCO Co., Ltd.), the measurement was performed by software using a sodium lamp light source at a wavelength of 589 nm.

(2) PLA 함량 (중량%)(2) PLA content (% by weight)

각 층의 두께비 및 사용된 각각의 수지의 밀도를 이용하여 전체 다층 필름에 대한 폴리락트산 수지의 함량을 계산하였다.The content of polylactic acid resin for the entire multilayer film was calculated using the thickness ratio of each layer and the density of each resin used.

(3) 열특성 ((3) thermal properties TgTg , , TcTc , , TmTm ) )

시차주사형열분석기(DSC analyzer, Perkin-Elmer사)를 이용하여 승온 속도 10℃/분으로 측정하여 최초 흡열 변화를 유리전이온도(Tg, ℃)로 하고, 그 다음에 나타나는 발열곡선의 피크점을 결정화 온도(Tc, ℃)로 하였으며, 그 뒤 계속해서 나타나는 흡열곡선의 피크점을 필름의 융점(Tm, ℃)으로 각각 나타내었다.Using a differential scanning thermal analyzer (DSC analyzer, Perkin-Elmer Co., Ltd.), the temperature rise rate was measured at 10 ° C / min, and the initial endothermic change was determined as the glass transition temperature (Tg, ° C), followed by the peak point of the exothermic curve. Was the crystallization temperature (Tc, ° C), and then the peak point of the endothermic curve which appears subsequently is represented by the melting point (Tm, ° C) of the film, respectively.

(4) (4) 열접착강도Thermal bond strength

샘플을 폭 15mm, 길이 150mm로 자르고 이를 제1수지층끼리 서로 접하게 한 후, 40psi/s의 열경사(heat gradient)의 조건으로 100℃에서 열접착을 하고, 이때 얻어진 샘플을 300m/min의 박리속도로 180o형 박리시험기(peel tester)로 측정하여 접착층이 박리될 때의 최대응력을 열접착강도로 나타내었다. The samples were cut into a width of 15 mm and a length of 150 mm and the first resin layers were brought into contact with each other, and then thermally bonded at 100 ° C. under a heat gradient of 40 psi / s, and the sample obtained at this time was peeled at 300 m / min. The maximum stress when the adhesive layer was peeled off was measured by a 180 o type peel tester at a speed, and was expressed as thermal adhesive strength.

(5) 증착강도 (5) deposition strength

진공챔버에서 알루미늄을 가열하고 용융상태로부터 증발시켜 제2수지층에 증착하여 박막을 800Å 두께로 형성시킨 후, 이 때 얻어진 샘플을 3M™ 테이프를 사용하여 증착층에 붙인 후에, 300m/min의 박리 속도로 180o형 박리시험기(peel tester)로 측정하여 증착층이 박리될 때의 최대응력을 증착강도로 나타내었다. After heating the aluminum in the vacuum chamber and evaporating from the molten state to deposit on the second resin layer to form a thin film of 800Åm thickness, the obtained sample was attached to the deposition layer using 3M ™ tape, and then peeled off at 300 m / min. The maximum stress when the deposited layer was peeled off was measured by the 180 o type peel tester at the rate of deposition strength.

(6) (6) 투습도Moisture permeability

상기 증착강도 측정시험에서 증착된 샘플을, 투습도측정장치(PERMATRAN-W Model 3/33, 히타치하이테크사)를 사용하여 증착면이 수분에 닿도록 장착하고, 38℃, 상대습도 90%에서 측정한 후 소프트웨어로 계산된 값을 투습도(단위: g/㎡·day·atm)로 나타내었다.The sample deposited in the deposition strength measurement test was mounted so that the deposition surface touched moisture using a moisture permeability measuring device (PERMATRAN-W Model 3/33, Hitachi Hi-Tech Co., Ltd.) and measured at 38 ° C. and a relative humidity of 90%. Then, the value calculated by the software is expressed as moisture permeability (unit: g / m 2 · day · atm).

(7) (7) 열수축률Heat shrinkage

샘플을 측정하려는 방향으로 길이 200mm, 폭 15mm로 재단하여 100℃로 유지되는 공기 순환 오븐 내에서 5분간 유지시킨 후 필름의 길이를 측정하여 아래의 계산식을 이용하여 종방향 및 횡방향의 수축률을 계산하였다.Cut the sample into 200mm length and 15mm width in the direction to measure the sample, hold it for 5 minutes in an air circulation oven maintained at 100 ℃, measure the length of the film, and calculate the shrinkage in the longitudinal and transverse directions using the following formula. It was.

수축률 (%) = (열처리 전 길이 - 열처리 후 길이) / 열처리 전 길이 x 100Shrinkage (%) = (length before heat treatment-length after heat treatment) / length before heat treatment x 100

Figure 112009072163170-PAT00004
Figure 112009072163170-PAT00004

상기 표 1의 결과로부터 본 발명의 실시예에 따르는 필름은 열접착성, 증착 후의 수분배리어성, 기계적 특성, 치수안정성 등 본 발명이 목적으로 하는 제반 물성이 고루 우수한 반면에, 본 발명의 범위에서 벗어나는 경우는 물성이 떨어짐을 알 수 있다.From the results of Table 1, the film according to the embodiment of the present invention has excellent properties such as heat adhesiveness, moisture barrier property after deposition, mechanical properties, dimensional stability, and the like, while in the scope of the present invention. In case of deviation, it can be seen that the physical properties are inferior.

이상, 본 발명을 상기 실시예를 중심으로 하여 설명하였으나 이는 예시에 지나지 아니하며, 본 발명은 본 발명의 기술분야에서 통상의 지식을 가진 자에게 자명한 다양한 변형 및 균등한 기타의 실시예를 이하에 첨부한 청구범위 내에서 수행할 수 있다는 사실을 이해하여야 한다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, It is to be understood that the invention may be practiced within the scope of the appended claims.

Claims (9)

결정성 폴리락트산계 중합체를 함유하는 기재층, 상기 기재층의 일면에 형성되고 D-락트산 함량이 4중량% 이상인 폴리락트산계 중합체를 함유하는 제1수지층, 및 상기 기재층의 다른 일면에 형성되고 지방족 또는 방향족 폴리에스터의 단독중합체 또는 공중합체를 함유하는 제2수지층을 포함하는 구성을 가지며, 전체 필름에 대한 폴리락트산계 중합체의 함량이 50 내지 99 중량%이고, 상기 제1수지층 및 제2수지층 중 적어도 한 층의 열접착강도가 500gf/inch 이상인, 다층 생분해성 폴리에스터 필름.A base layer containing a crystalline polylactic acid polymer, a first resin layer formed on one side of the base layer and containing a polylactic acid polymer having a D-lactic acid content of 4% by weight or more, and formed on the other side of the base layer And a second resin layer containing a homopolymer or copolymer of aliphatic or aromatic polyester, wherein the content of the polylactic acid polymer is 50 to 99% by weight based on the total film, and the first resin layer and The multilayer biodegradable polyester film, wherein the thermal adhesive strength of at least one of the second resin layers is at least 500 gf / inch. 제1항에 있어서, The method of claim 1, 상기 필름은, 상기 제1수지층 및 제2수지층 중 적어도 한 층에 알루미늄을 증착했을 경우의 증착강도가 200gf/inch 이상인 것을 특징으로 하는, 다층 생분해성 폴리에스터 필름. The film is a multilayer biodegradable polyester film, characterized in that the deposition intensity when the aluminum is deposited on at least one of the first resin layer and the second resin layer is 200 gf / inch or more. 제1항에 있어서, The method of claim 1, 상기 필름은, 상기 제1수지층 및 제2수지층 중 적어도 한 층에 알루미늄을 증착했을 경우의 투습도가, 38℃ 및 상대습도 90%의 조건에서 20g/㎡·day·atm 이 하인 것을 특징으로 하는, 다층 생분해성 폴리에스터 필름.The film has a water vapor transmission rate of 20 g / m 2 · day · atm or less under conditions of 38 ° C. and 90% relative humidity when aluminum is deposited on at least one of the first resin layer and the second resin layer. Multilayer biodegradable polyester film. 제1항에 있어서, The method of claim 1, 상기 필름은, 100℃, 5분의 열풍조건에서의 종방향 및 횡방향의 열수축율이 20% 이하인 것을 특징으로 하는, 다층 생분해성 폴리에스터 필름.The film has a multi-layer biodegradable polyester film, characterized in that the heat shrinkage in the longitudinal and transverse directions at 100 ° C. and hot air conditions for 5 minutes is 20% or less. 제1항에 있어서, The method of claim 1, 상기 제2수지층에 포함되는 지방족 폴리에스터는, 하기 화학식 1 내지 3 중 하나 이상의 반복단위를 포함하는 단독중합체 또는 랜덤블록 공중합체인 것을 특징으로 하는, 다층 생분해성 폴리에스터 필름:Aliphatic polyester included in the second resin layer is a multi-layer biodegradable polyester film, characterized in that the homopolymer or random block copolymer containing one or more repeating units of the formula 1 to 3: [화학식 1][Formula 1]
Figure 112009072163170-PAT00005
Figure 112009072163170-PAT00005
 [화학식 2][Formula 2]
Figure 112009072163170-PAT00006
Figure 112009072163170-PAT00006
 [화학식 3](3)
Figure 112009072163170-PAT00007
Figure 112009072163170-PAT00007
 상기 화학식 1 및 2에서, R1은 C1-3알킬이고, R2는 C1-7알킬이다.In Chemical Formulas 1 and 2, R 1 is C 1-3 alkyl, and R 2 is C 1-7 alkyl. 제1항에 있어서, The method of claim 1, 상기 제2수지층에 포함되는 지방족 폴리에스터는, 폴리하이드록시부티레이트(polyhydroxybutyrate, PHB), 폴리-3-하이드록시발러레이트(poly-3-hydroxyvalerate, PBV), 폴리하이드록시부티레이트 발러레이트(polyhydroxybutyrate valerate, PHBV), 폴리-3-하이드록시부티레이트-코-3-하이드록시발러레이트(poly-(3-hydroxybutyrate-co-3-hydroxyvalerate), P(3HB-co-3HV)), 폴리-3-하이드록시부티레이트-코-3-하이드록시헥사노에이트(poly-(3-hydroxybutyrate-co-3-hydroxyhexanoate), P(3HB-co-3HH)), 및 폴리글리콜산(PGA)으로 이루어진 군으로부터 선택되는 1종 이상인 것을 특징으로 하는, 다층 생분해성 폴리에스터 필름.The aliphatic polyester included in the second resin layer may include polyhydroxybutyrate (PHB), poly-3-hydroxyvalerate (PBV), polyhydroxybutyrate valerate, and polyhydroxybutyrate valerate. , PHBV), poly-3-hydroxybutyrate-co-3-hydroxyvalerate, P (3HB-co-3HV), poly-3-hydroxy Oxybutyrate-co-3-hydroxyhexanoate (poly- (3-hydroxybutyrate-co-3-hydroxyhexanoate), P (3HB-co-3HH)), and polyglycolic acid (PGA) Multilayer biodegradable polyester film characterized by the above-mentioned. 제1항에 있어서, The method of claim 1, 상기 제2수지층에 포함되는 방향족 폴리에스터는, 방향족 디카복실산과 C1-10알킬렌글리콜이 중축합된 수지인 것을 특징으로 하는, 다층 생분해성 폴리에스터 필름.The aromatic polyester contained in the second resin layer is a multilayer biodegradable polyester film, characterized in that the resin is a polycondensation of an aromatic dicarboxylic acid and C 1-10 alkylene glycol. 제1항에 있어서, The method of claim 1, 상기 필름은, 각각의 원료 수지를 이용하여 공압출 공정 및 이축 연신 공정을 거쳐 제조되는 것을 특징으로 하는, 다층 생분해성 폴리에스터 필름.The film is produced through a co-extrusion process and a biaxial stretching process using the respective raw material resin, multilayer biodegradable polyester film, characterized in that. 제1항 내지 제8항 중 어느 한 항에 따른 다층 생분해성 폴리에스터 필름을 포함하는 포장재.A packaging material comprising the multilayer biodegradable polyester film according to any one of claims 1 to 8.
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